Process for breaking petroleum emulsions employing certain polyepoxide treated derivatives obtained by reaction of monoepoxides with resins



detail, and formaldehyde; (2) oxyalkylation of the con- '-described in detail; and (3) oxyalkylation of the previpolyepoxides, hereinafter described in detail, and cogener- 2,771,43l Patented Nov, 20, 1956 f1 rates Patent ice t ained by the elimination of the aldehyd'ic oxygen atom;

Unite 2,771,431 the divalent radical PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING CERTAIN PQLY-EPOXIDE 11 H TREATED DERIVATIVES OBTAINED BY REAC- the divalent TION on MONOEPOXIDES WITH RESINS Melvin De Groote, University City, and Kwan-Ting Shen,

Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware radical, the divalent sulfone radical, and the divalent 'monosulfide radical S the divalent radical f lffg ggg g2 1953 CHzSCH2-, and the divalent disulfide radical ss;

and R10 is the divalent radical obtained by the elimination 20 Claims. (Cl. 252-338) of a hydroxyl hydrogen atom and a nuclear hydrogen 15 atom from the phenol The present invention is a continuation-in-part of our co-pending application, Serial No. 305,079, filed August 18, 1952, now abandoned. Our invention provides an economical and rapid procl ess for resolving petroleum emulsions of the water-inoil type that are commonly referred to as cut oil," roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in stituent member having not over 18 carbon atoms. a more or less permanent state throughout the oil which A further limited aspect of the invention is represented constitutes the continuous phase of the invention. by the use of such products wherein the oxyalkylated It also provides an economical and rapid process for resin condensate is reacted with a member of the class of separating emulsions which have been prepared under (a) compounds of the followingformula controlled conditions from mineral oil, such as crude oil RX and relatively soft Waters or Weak brines. Controlled OH-CHr-O. R,

emulsification and subsequent demulsification under the E20 conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pi eline oil. wherein R is essentially an aliphatic hydrocarbon bridge,

Attention is directed to two co-pending De Groote each n indepe y has one Of the Values 0 t0 and 1 applications, Serial No. 310,552, filed September 19, is an alkyl radical containing from 1 to 4 carbon atoms 1952, now patent No. 2,695,888, and Serial No. 333,387, or even 12 carbon atoms, and (b) cogenericallyassociated filed January 26, 1953. These two applications describe compounds formed in the preparation of (a) preceding, hydrophile products obtained by the oxyalkylation of including monoepoxides. products obtained by condensing certain phenol-aldehyde Reference herein to being thermoplasticor non-thermoresins with basic hydroxylated secondary monoamines 4,0 setting characterizes products as being liquids at ordinary and formaldehyde. temperature or readily convertible to liquids by merely The present invention is concerned with the use of heating below the point of pyrolysis and thus differentiates products obtained by reacting said oxyalkylated derivathem from infusible resins. Reference to being soluble tives of the kind just described with a phenolic polyepoxide in an organic solvent means any of the usual organic solof the kind previously described in our aforementioned vents, such as alcohols, ketones, esters, ethers, mixed solco-pending application, Serial No. 305,079. vents, etc. Reference to solubility is merely to differenti- Thus the present invention is concerned with the ate from a reactant which is not soluble and might be not breaking of water-in-oil emulsions by the use of products only insoluble but also infusible. Furthermore, solubilof reaction obtained by a 3-step manufacturing process ity is a factor insofar that it is sometimes desirable to involving (1) condensing certain phenol aldehyde resins, dilute the compound containing the epoxy rings before hereinafter described in detail, with certain basic hydroxreacting with the monoepoxide-derived product. In such ylated secondary monoamines, hereinafter described in instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ously ox-y'alkylated resin condensate with certain phenolic ethyleneglycol diethylether, diethyleneglycol diethvlether and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a comin which R, R", and R' represent hydrogen and hydrocarbon substituents of the aromatic nucleus, said subdensation product with certain monoepoxides, hereinafter ically associated compounds formed in their preparation.

A more limited aspect of the present invention is concerned with the use of such products of reaction obtained wherein the oxyalkylated resin condensate is reacted with a member of the class of compounds of the following formula:

O H O in which R represents a divalent radical selected from pound has two or more oxirane rings they will be referred the class of ketone residues formed by the elimination to as polyepoxides. They usually represent, of course, of the ketonic oxygen atom and aldehyde residues ob- 1,2-epoxy rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon a oms and is formally described as l,2-epoxy-3,4-epoxybutane (l,2,3,4 diepoxybutane).

It well may be that even though the previously sug gested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric phenols containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins.

Having obtained a reactant having generally 2 expoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any oxyalkylated phenol-aldehyde resin condensate by virtue of the fact that there are always present either phenolic hydroxyl radicals or alkanol radicals resulting from the oxyalkylation of the phenolic hydroxyl radicals; there may be present reactive hydrogen atoms attached to a nitrogen atom or an oxygen atom, depending on whether initially there was present a hydroxylated group attached to an amino hydrogen group or a secondary amino group. In any event there is always a multiplicity of reactive hydrogen atoms present in the oxyalkylated amine-modified phenol-aldehyde resin.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a moi of the oxyalkylating agent, i. e., the compound having two oxirane rings and an oxyalkylated amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of two moles of the oxyalkylated amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their weight of 5% gluconic acid at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, 80 parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone. As oxyalkylation proceeds the significance of the basicity of any nitrogen group is obviously diminished.

For purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those products which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufficiently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience, what is said hereinafter will be divided into nine parts with Part 3, in turn, being divided into three subdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

H H H oxyalkylated (oxyalkylated condensate) condensate) groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form such as they acetate, chloride, etc. differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not. only does this property serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or The purpose in this instance is to i Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxides, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin Which is subjected to modification by condensation reaction to yield an amine-modified resin;

Part 5 is concerned with appropriate basic hydroxylated secondary monoamines which may be employed in the preparation of the herein-described amine-modified resins;

Part 6 is concerned with reactions involving the resin, the amine and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation with monoepoxides; 7

Part 7 is concerned with the oxyalkylation of the products described in Part 6, preceding;

arr 1.

Part 8 i aonc rn c ns nv in th two pre edi ypes o materials a d amp sfibta ned by such-reactions. Generally sp raking, this involves nothing 1 nore than a reaction between two moles of a previouslyprepared oxyalkylated amine-modified phenol-aldehyde resin condensate as described and one mole of a polyepoxide so asto yield a new and larger resin molecule .or: c mpa abl p d Part 9 is concerned with the resolution of petroleum emulsions ofthe water-in-oil type by means of the previously described chemical compounds or reaction products.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquids or low-melting solids. Indeed, they tend .to form thermosetting resins or insoluble materials.

Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides andas free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the formof diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the ,epoxides usually results in the formation of a cogeneric mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be .used for practicalreasons are either monomers with some-small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actua lly, it is our preference to use those which are commerciallyavailable and for most practical purposes it means instances Where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known glasses may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in othe ex p e Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our prefr c is to pro u e .themby means of th saishlor' dr media re r in, ls-t i ubs ently:

One epoxide which can be purchased in the open market and contains only a modest arnount of pol yn' ers corresponds to the derivative of bis pflhenol A. it can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the -=following structure is preferred as the epoxide reactant and will be used forillustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer andhigherpolymers are satisfactory. The formula for this compound is stant part, to .wit, Part 1, and in succeeding parts, the

text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be in;- material if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound for the other would be required. Thus,-what is said hereinafter, although directed to one class or a few classes, applies with equal force and effect to the other classesof epoxide reactants.

If sulfur-containing compounds are prepared theyshould be freed from impurities with considerable care for the reason that any time that a low-molal sulfur-containing compound can react with epichlorohydrin there may he formed a by-product in which the chlorine happened to be particularly reactive nad may represent a product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration,

PART 2 The polyepoxides and particularly the diepoxides can be. derived by more thanonerneth'odas, for example, the use of epichlorohydrin or glycerol dich'lorohydrin. If a product such asbis-phenol A is employed the ultimate compound in monomeric form employed as a reactant in the present invention has the following structure:

Treatment with epichlorohydrin, for example, does not yield this product initially but there is an intermediate produced which can be'indicated by the following structure:

I i l H g I 01 H OH; H Cl Treatment with alkali, of course, forms the epoxy ring. A number of problems are involved in attempting to produce this compound free from cogeneric -materials of related composition. The difiiculty stems from a number of sources and a few of the more important ones are as follows:

(1) The closing of the epoxy ring involves the use of caustic soda or the like which, in turn, is an efiective catalyst in causing the ring to open in an-oxyalkylation reaction.

. 7 8 Actually, what may happen for any one of a number Some reference has been made to the presence of of reasons is that one obtains a product in which there a'chlorine atom and although all elfort is directed towards ,is only one epoxide ring and there may, as a matter of the elimination of any chlorine-containing molecule yet fact, be more than one hydroxyl radical as illustrated by it is apparent that this is often an ideal approach rather the following compounds: 5 than a practical possibility. Indeed, the same sort of reactants are sometimes employed to obtain products in H H H (3H3 H H H which intentionally there is both an epoxide group and a Ho -c-o-oC oC 0oc--oH chlorine atom present. See U. S. Patent No. 2,581,464,

. H (3H3 H 4, dated January 8, 1952, to Zech.

' 10 For purpose of brevity, without going any further, the .9 next formula is in essence one which, perhaps in an ideal- H CH3 H H H ized Way, establishes the composition of resinous prod- C ucts available under the name of Epon Resins as now H 1 H l sold in the open market. See, also, chemical pamphlet 15 entitled Epon Surface-Coating Resins, Shell Chemical (2) Even if one starts with the reactants in the pre- Corporation, New York city. The word Epon is a regferred ratio, to wit, two parts of epichlorohydrin to one istered trademark of the Shell Chemical Corporation.

(3H1 OH: a CH; (IJHI 05 /OH 1/ I on, on: part of bis-phenol A, they do not necessarily so react For the purpose of the instant invention, n may repreand as a result one may obtain products in which more sent a number including zero, and at the most a low than two epichlorohydrin residues become attached to a 3 number such as 1, 2 or 3. This limitation does not single bis-phenol A nucleus by virtue of the reactive exist in actual efforts to obtain resins as differentiated hydroxyls present which enter into oxyalkylation reacfrom the herein described soluble materials. It is quite 'tions rather than ring closure reactions. probable that in the resinous products as marketed for (3) As is well known, ethylene oxide in the presence coating use the value of n is usually substantially higher. 'of alkali, and for that matter in the complete absence of Note again what has been said previously that any water, fonns cyclic polymers. Indeed, ethylene oxide can formula is, at best, an over-simplification, or at the most produce a solid polymer. This same reaction can, and represents perhaps only the more important or principal at times apparently does, take place in connection with constituent or constituents. These materials may vary compounds having one, or in the present instance, two from simple non-resinous to complex resinous epoxides substituted oxirane rings, i. e., substituted 1,2 epoxy rings. 40 which are polyether derivatives of polyhydric phenols Thus, in many ways it is easier to produce a polymer, containing an average of more than one epoxide group particularly a mixture of the monomer, dimer and trimer, per molecule and free from functional groups other than than it is to produce the monomer alone. epoxide and hydroxyl groups.

(4) As has been pointed out previously, monoepoxides -In summary then in light of What has been said, commay be present and, indeed, are almost invariably and pounds suitable for reaction with amines may be sum inevitably present when one attempts to produce polymarized by the following formula:

OO,-O O R n- OO'O'-O O R OOOO a EH, III [1 Ill m n, IL 1 H.

I I u! Ii! 0H lL ln RI! RI! I! R R R epoxides, and particularly diepoxides. The reason is the H or for greater simplicity the formula could be restated one which has been indicated previously, together with thus:

o o-o- CR1[R],.R10COO OR1-[R]nRiO-G-C C H2 E H2 z 6H H2 H: H H:

the fact that in the ordinary course of reaction a diepoxide, in which the various characters have their prior signifi u h a canoe and in which R10 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a H H H E H H H nuclear hydrogen atom from the phenol ?C '7 0 CH3 0 OH v may react with a mole of bis-phenol A to give a monol I epoxy structure. Indeed, in the subsequent text immediatel'y following reference is made to the dimers, trimers and tetramers in which two epoxide groups are present. in. which R', R", and R' represent a member of the Needless to say, compounds can be formed which corclass consisting of hydrogen and hydrocarbon substituents respond in every respect except that one terminal epoxide of the aromatic nucleus, said substituent member having group .is absent and in its place is a group having one not over 18 carbon atoms; n represents an integer selectchlorine atom and one hydroxyl group, or else two hyed from the class of zero and 1, and n represents a droxyl groups, or an unreacted phenolic ring. a 7 5 whole number not greater than 3.

PART 3 Subdivision A 10 H :Bu-relwbya'wayiof illustration, the following diepoxides, or rdi-gl-ycidyl -ethers --as they are sometimes -termed, are included for purpose of illutstlzaliqn- Eliss p m fiule compounds are described in the two patents just-'men- The preparation of the 'diepoxy derivatives ofthe di- 5 ti d,

TABLE I Ex- Patent ample Dipheno] Diglycldyl ether refer number ence Di(epoxypropoxyphenyl)methane 6, 6

- Digepoxypr opoxyphenylgdiethylmethane".. Di epoxypropoxyphenyl Di(epoxypropoxyphenyl)methylp lenb'lmethan Di(epoxypropoxyphenyl)ethylphenylmethane 506, 4 D1(epoxypropoxyphenyl)propyl hanylm'cthane ,506,486 C Di(ep0 yDrop0xyphenyi)butylp enylmethane- 506, 486 a s 4) o Qs I 1(enQ yp p yn e s' y ethramarub-7.. w ,.& r148 12A..- (CHzGeHr)C(CH;) (CsHOH)1 Di(epoxypropoxyphenyl)tolylmethylmethane 506, 486 13A-.... Dihydroxy diphenyl 4,44115(2,3-epoxypropoxy)diphenyl 2, 530, 353 14A (CH:)C(C4H5.CeHsOH)a 2,2-bis(4-(2,3-epoxypropoxy)Z-tertiarybutyl phenyDpropane... 2, 530,353

phenols, which are sometimes referred to as diglycidyl ethers, have been described in a number of patents. For

" convenience, reference will be made to two only; to wit,

aforementioned U. S. Patent 2,506,486, and aforementioned U, S. Patent No. 2,530,353.

Subdivision B As to the preparatiomof lowl-molaLpolymeric ep0xides or: mixtures reference is made to aforementioned U. S. Patents ENOs..2;5.75,558 and 2,582,985.

In light of U S. Patent No. 2,515,558, "the following examples can be specified by reference to the'formula 30 therein provided one still bears in mind it is in essence an over-simplification.

TABLE II 1 I o o-c- -o R '-.[R .-R1o-o-:-o-c- -R1-[B1,.R10-c-co H: H H: H: (g H: L Hz H H,

, H n, (in which the characters have their prevlous significance) Example R10lrom HRiOH -R- n n Remarks number 1 B1 Hydroxy benzene 1 0,1,2 5' Phenol -known as bis-phenol A. 'Low polymeric mixture about 'y or more where 'n=0, remainder largely where =1, some where 1!;2.

':-B2. l--..;do 0,1,2 rPhenolknown asbis-phcnolB. Seenote n regarding B1 above.

133 0rthobutylphenoL,,,,' 1 0,1,2 :Even though 11 is prelerably 0, yet the usual reaction product might well contain materials wheremt. is 1, or t0,a i "lesser degree'2.

B4 Orthoamylphenol 1 0,1,2 Do.

a B5 -erthooctylphanol .4 v 1 0,1 ,2. Do. "I c B6 0rthononylphenol ll =0;1 '-'-'Do. a =4 I r JB'Z... Orthododecylphenol "-1 Do.

B8 Metacresol '-1 10,152 See- -prior. nc te. "This-phenol used as 1 initial material is known. asbis-phenol V V C. For other suitable bis phenols see h U18. Patent -2;564,191.

' Tan LE: 1 1= (continued) 'Eianiple R 1O -fro'm HR H r n Remarks 4 I b r ,3. t I

139 do on, 0,1,2 ee prior my (3H1 i B Dibntyl(ortho'pare) phenol. 1% 0,1,2 Do.

, H B11 Diamyl (ortho-para) phenol. g 6,1,2 Do.

B12 Dioctyl (ortho-para) phenolg 0,1,2 D0.

B13 Dlnonyl (ortho-para) phenol. g

B14 Diamyl (ortho-pem) phenolg 0,1,2 D0- B15 do H 0,1,2 Do.

Bl6 Hydroxy benzene. i I (I) 0,1,2 D0

B17 Diamyl phenol (ortho-para)- SS- 0, 1,2 D0 1318 --do s- 0,1,2 Do.

B19 Dibutyl phenol (ortho-para), g I 0, 1,2 D0 H, H t

320.-.." ...do H n 0,1,2 D6."

' -oo l B21 Dinonylphenol (ortho-para)- ICI g 0,1,2 D0. 7 H n B22 Hydroxy benzene (H) 0,1,2 D0- I C B23 .'d0 None 0,1,2 Do.

B24 Ortho-isopropyl phenol 7 CH; 0,1,2 Seeprlor note. As to preparation ot 4,4'- v l isopropylidene bis-(2lsopropylphenol) C-- see U. 8. Patent No. 2,482,748, dated Sept. 27, 1949, to Dietzler. CHI

B25 Para-act l henol CH S-CEf 0 1 2 See prior note. (As to preparation 0! the y p ri phenol sulfide 506 U. 8. Patent No. 2,488,134, dated Nov. 15, 1949, to Mikeska et a1.) B26 Hydroxybenzene CH; 0,1,2 See prior note. (As tolpreparation oi the phenol sulfide see 8. Patent No. -o- 2,520,545.) 1

+11: 0 (IJIH5 Subdivision C I The prior examples have been limited largely to those in which there is no divalent linking radical, as in the case of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly aketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regardless of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be r'eadilyconverted-to a suitable polyepoxide, and particularly diepoxide, reactant. j I

As previously pointed ,out the initial phenol may be substituted, and the substituent group in turn maybe a cyclic group such as the phenyl group or cyclohexyl group 76 as in the instance ot cyclohexylpheno1 or phenylphenol. Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

Similar phenols which are monofunctional; for instance,

paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, may beemployed in reactions previously referred to, foriin'stance, with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for subsequent reaction with epichlorohydrin, etc.

Other samples include:

OH OH l R1 E0111 OH; CH:

wherein R1 is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R2 is-a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, *aralkyl, and-alkaryl groups, and wherein-said alkyl group contains at'leastf3 carbon atoms. See U. S. Patent No. 2,515,907.

OaHn 05 11 in which the -'C5Hu groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

HO OH wherein R is a member of the group consistingof allgyl,

-and alkoxy-alkyl radicals containing from 1 to'S carbon atoms, inclusive, and aryl and chloraryl radicals of'the benzene series. See U. S. Patent No. 2,526,545.

wherein R1 is.a substituent selected from the class con- .sistingof secondary butyl. and tertiary butylgroups and R2 isa substituent selected from'the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. "See p U. S. Patent No. 2,515,906.

"Nos.

CH=OH 0 .g

J. ll}

| OH: OH:

See us. Patent 'No. 2,515,908.

As to:sulfides,the'followingcompound is of interest:

OH 'O See U. S. Patent No. 2,331,448.

As-to descriptions 'of various suitable phenol sulfides, reference is made to the following patents: U. S. Patents 2,246,321, "207,719, 2,174,248, 2,139,766, 2,244,021, and 2,195,539.

As to sulfones,sedUfSJPatent No; 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or some 'other'aldehyde, particularly compounds in which R5 is a methylene radical; era-substituted methyl- 'ene radicalwhichrepresentstheresidue of analdehyde and is'preferably' the unsubstituted methylene radical derived from formaldehyde. See U. SJPa'tentNo. 2,430,002.

See also U. S. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides, the disulfides, and the vpolysulfides. The following formula represents the various dicresol sulfides of this invention:

on on: on.

in which R1 and R2 are alkyl groups, the "sumrof whose carbon atoms equals 6 to about'20, and Ri'an'd R2 each preferably contains 3 to about '10 carbon 1atoms,'.and:x is 1 to 4. The term sulfides as used in this text, there fore, includes monosulfide,.disu1fide, and polysulfides.

PART 4 It is Well known that onecan readily purchase on the open market, or prepare fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by' the formula on n In the above formulan represents asmall whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 M12 units, particularly when .the resin is subjected to heating under -a vacuum. as described in the literature. A

- the aldehyde, or any one 'mole of the amine may comlimited sub-genus is in the instance of low molecular weight polymers Where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4 R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms such as a butyl, 5 amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organicsolvent-soluble does not .10 mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin which is not 5 soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and non-oxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser. I

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resins having an average molecular weight corresponding .toat least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in' regard to methylol-forming reactivity, are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol, and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not" more than 24 carbon atoms, and substituted in the 2,4, 6 position. If one selected a resin of the kind just described previously and reactedapproximately one mole of the resin with two moles of formaldehyde and two moles of a basic :nonhydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thusz' R" on: n

OH OH In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, .2 moles of amine may combine with one mole of 75 1 16 bine with the resin molecule, or even to a. very slight extent, if at all, 2 resin unitsmay combine without any amine in thereaction product, as indicated in the following formulas:

011 V on on on on n I r n H H 13 o oo o o n n ,H n n R R- 1 a As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thusz' OH" I- on in which R'" is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,638. Resins cans be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. .It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong .acid should be neutralized. similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and asl muchas a few l0ths of a percent. Sometimes modj erat'e'inerease lIICaUSfiCISOdZt and caustic potash may be "used. Howevenf. the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer i. e., one having just 3- units, or just 4 units, or just 5 units, or just 6'units,etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example,-3.5, 4.5 or 5.2.

.eln, the actual, manufacture of the resins we found no reason' for using other than thosewhich are lowestin price and mostIre'adiIy' availablecommercially. For purposes of convenience suitable. resins are characterized in the following table:

TABLE III M01. wt Ex- R' of resin ple R Position derived n molecule number of R from- (based on n+2) Phenyl. Para Formal- 3. 5 992. 5

dehyde Tertiary'buty1 do d 3. 5 882. 5 Secondary butyL-.. Ortho..- do. 3. 5 882. 5 Oyclohexyl do." 3. 5 1', 025.5 Tertiary amyl 3. 5 959. 5 Mixed secondary do 3. 5- 805. 5

and tertiary'amyl.

yl do 3. 5 805.5 3. 5 1, 036. 5 3. 5 1, 190. 5 3. 5 1, 267. 5 3. 5 1, 344. 5 3. 5 1, 498. 5 Tertiary butyl 3. 5 945. 5

hyde Tertiary arnyl 3. 1,022. 5 Non .do 3. 5 1, 330. 5 Tertiary butyl; Butyr- 3. 5 1, 071. 5

aldehyde Tertiary amy1 do 3. 5 1, 148. 5 Nonyl do 3. 5 1, 456. 5 Tertiary butyl Propion- 3. 5 1, 008. 5

4. 2 1, 083. 4 4. 2 1, 430. 6 4. 8 1, 094. 4 4. s 1, 139. 6 4. 8 1, 57011 Tertiary amyi 1. 5 604. 0 Cyclohexyll. 1. 5' 646$ 0 Y Hexyl 1. 5 653. 0 1. 5 688.0

PART 5' As has. been pointed out previously the amine herein employed as a reactant is a basichydroxylated secondary monoamine whose composition is indicated thus:

in which- R represents a monovalent alkyl, alicyclic, aryla'lkyl radical: which may be-heterocyclic in' a few instancesas in a secondary amine derived from furfurylamineby reaction. of'ethylene' oxide or propylene oxide. Further-- more, at least one of the radicals designed by R must' have at least one hydroxyl radical. A large number of secondary amines are available and may be suitably emplayed as reactants for the present purpose. Among Others, one may employ diethanolamine, methyl ethanolamine, dipropanolamine and ethylpropanolamine. Other suitable secondary amines are obtained, of course, bytaking-any suitable primary amine, such as an alkylamine, an arylalkylarnine, or an alicyclic amine, and treating the amine with one mole of an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide; Suitable primary amines which can be so converted into secondary amines, include butyl'amine, amylamine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine etc. In other instances secondary amines which have at least one hydroxyl radical can be treated similarly with an oxyalkylating agent, or, for that matter, with an alkylating agent such as benzylchloride, esters of chloroacetie acid, alkyl bromides, dimethylsulfate esters of sulfonic-acid, etc., so as to convert the primary amine into a secondary amine- Among. others, such amines include 18 Z-amino-l-butan-ol, Z-amino-Z-methybl propanol, Z-amino-2-methyl-1,3-propanediol, Z-amino 2 ethyl-1,3-propanediol, and tri-(hydroxymethyl)-aminomethane. Another example of such amines is illustrated by 4-amino-4- methyl-Z-pentanol.

Similarly one can prepare suitable secondary amines which have not only a hydroxyl group but also one or more divalent oxygen linkages as part of an ether radical. The preparation of such amines or suitable reactants for preparingv them has been described in the literature and particularly in two- United States patents, to wit, U. S. Patents Nos. 2,325,514 dated July 27, 1943 to Hester and 2,355,337 dated August 8, 1944 to Spence. The latter patent describes typical haloalkyl ethers such as CHaO 0211401 CHgCH2 CH2 CH-CHzO 021140 CQHLBI CzHsO CzHrO (EH40 CzH4O 0311401 Such haloalkyl ethers can be reacted with ammonia or with. a primary amine, such as ethanolamine, propanolamine, monoglycerylamine, etc., to produce a secondary amine in which there is not Only present a hydroxyl radical but a repetitious ether linkage. Compounds can be readily obtained which are exemplified by the following' formulas:

H 0 C 2H4 (CH O'CHzCHgCHzCHzCHCHz) H O C $114 or comparable compounds having two hydroxylate'd groups of diiferent lengths as in- (HOOHzGHzOCHaGHaOCHaCHa) HOC2H4 Other examples of suitable amines include alpha-methylbenzylamine and monoethanolamine; also amines obtained by treating cyclohexylmethylamine with one mole of an oxyalkylating agent as previously described; betaethylhexyl-butanolamine, diglycerylamine, etc. Another type of aminewhich is of particular'interest because it includes a very definite hydrophile group includes sugar amines such as glucamine, galactarnine and fructamine, such as N hydroxyethylglucamine, N-hydroxyethylgalactamine, and N-liydroxyethylfructamine.

Other suitable amines may be illustrated by r HO.CHz.("J.OHiOH r rn HO.CH2.C.'CH2OH' See, also, corresponding hydroxylated amines which can be obtained from rosin or similar raw materials and described in U. S. Patent No. 2,510,063 dated June 6, 1950, to Bried. Still other examples are illustrated by treatment of certain secondary amines, such as the following, with a mole of an oxyalkylating agent as described; phenoxyethylamine, phenoxypropylamine, phenoxyalphemethylethylamine, and" phenoxypropylamine.

Other procedures for production of suitable compounds having a hydroxyl group and a single basic aminonitrogen atom can be obtained from any suitable alcohol or the like by reaction with a reagent which contains an epoxide group and a secondary amine group. Such reactants are described, for example, in U. S. Patents Nos. 1,977,251 and 1,977,253, both dated October 16, 1934, to Stallmann. Among the reactants described in said latter patent are the following:

PART 6 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is ditficult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-aminealdehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heat-reactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since tem peratures up to 150 C.. orv thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However for purpose of clarity the following details are included.

. A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solventv and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However if desirable, one can use an oxygenated solvent such as a lowboiling alcohol, including ethyl alcohol, methyl acohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mix ture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difiicult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as Water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation then, obviously, the alcohols should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course is an advantage for reasons stated.

The products obtained, depending on the reactants selected, may be water-insoluble, or water dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidifiedvehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for'reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as faras it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein'described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any casewhere it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantagev in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitason that reaction: probably takes place principally at the interfaces and;the morevigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected' solvent, such as. benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely dissolved. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the amine is added and stirred. Depending on the amine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formalde hyd'e solution as added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of' a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example, 35 C. or slightly lower provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreactedformaldehyde loss.

On a large scale if there is any difficulty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave. and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difliculties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to. the preferred method of reaction and particularly from the standpoint of laboratory procedure employing .a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C., for 4 or hours,

or at the most, up to 24. hours, wecan complete thereaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of amine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then perm-it'the temperature to rise to somewhere about 100 C., and generally slightly above. 100 C., and below 150 C., by eliminating the solvent or part of the solvent. so the reaction m-ass stays within this predetermined range. This period of heating and refluxing, after the water isel-iminated is continued until the reaction mass is homogeneous and then for one to. three hours longer. The removal ofv the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary amine and 2 moles 22 of. formaldehyde. trace; of caustic-as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess offormaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surface-activity particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted amine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration.

Example 1b The phenol-aldehyde resinis the one that has been identified previously as Example 2a. it was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an aver-age of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e-., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding were powdered and mixed with 700 grams of xylene. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C. and 210 grams of dietha-nolamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde used was a 37% solution and 160 grams were employed which were added in about 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C. for about 21 hours. At the end of this period of time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time and the presence of unreacted formaldehyde noted. Any nnreacted formaldehyde seemed to disappear within approximately 3 hours after the refluxing was started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached about C. The mass was kept at this higher temperature for about 3% hours and reaction stopped. During this time any additional water which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on .a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or :a tacky resin. The :overall reaction time was a little over 30 hours. In other instances it has varied from approximately 24 to 36 hours. The time can be reduced by cutting the low temperature period to about 3 to 6 hours.

Note that in Table IV following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final prod- Insome instances we have added. a

uce reflux for several hours somewhere 'lin'the range of 145 to 150 C. or thereabouts. Usually the mixture scription of the procedure is omitted and the process will: simply be illustrated by the following examples:

Example The oxyalkylation-susceptible compound employed is the one previously described and designated as Example TABLE IV Strength of 7 Rear:- Reac- Max. Ex. Resin Amt, formal- Solvent used tiou tlon dis- No. used grs. Amine used and amount dehyde and amt. temp, time, till.

soln. and 0. (hrs.) tern amt.

882 Diethanolamine, 210 g 31%, 162 g; Xyl n 700 m 2H6 32 137 .480 Diethanolamlne, 105 37%, 81 g Xylene, 450 g. 21-23 28 150 638 do do Xylene, 600 g. -22 36 145 D prop 30%, 100 g Xylene, 400 gm. 20-23 34 146 d do1 Xylene, 450 g 21-23 24 141 633 do do Xylene, 600 g 21-28 24 145 882 Ethylethanolamine, 178 g" 37%, 162 g... Xylene, 700 g 20-26 24 152 480 Ethylethanolamine, 89 g". 37%, 81 g Xylene, 450 g. 24-30 28 151 633 do do Xylene, 600 gm. 22-25 27 147 473 Cyclohexylethauolamine, 143 g. 30%, 100 g... Xylene, 450 g 21-31 31 146 511 do 37%, 81 g. d0 22-23 36- 148 665 do "do Xylene, 550 g. 20-24 27 152 C2H$O0IH4OOIH4 13b 2a 441 NH, 176 g -d0 Xylene, 400 g 21-25 24 150 C2H5002H4OC2H4 14b 5a 480 NH, 176 g -do Xylene, 450 g. 20-26 26 146 VHOOIH! i GQHOCIH4OOIHL i 1611--.. 9a. 595 NH, 176 2 .do Xylene, 650 gm. 21-27 30 147 HOCzHa HOClHOCiHAOCflHA 16b. 2a 441 1 NH, 192 g do Xylene, 400 g.... 20-22 30 148 HOO|H4 HOCnHtOCaHAO GaHA 17b 5a 480 NH, 192 g do do 20-25 28 150 HOCIHtOCiHAOCiHA 18b 1%.... 511 NH, 192 g d0 Xylene, 500 g 21-24 32 149 TIOCzHtOCsHaOCzHt 19b. 2212.--- 498 NH, 192 g d0 Xylene, 450 g 22-25 32 153 HOOsHt I OH:(OC:H4)1

20b 2311.--- 542 NH, 206 g .Q 30%, 100 g.- Xylene, 500 gm. 21-23 36 151 HOG/1H4 I C a( 2 4):\

21b a. 547 NH, 206 g do ...do.. 25-30 34 148 HOOQHA I( A)t 22b 2a.-." 441 NH, 206 g -do Xylene, 400 gm 22-23 31 146 HOCflH4 23b 260.. 595 Deeylethanolamlne, 201 g 37%, 81 g. Xylene, 500 g.... 22-27 24 145 24b 27a 391 Decylethanolamine, 100 g 30%, g. Xylene, 300 gm. 21-25 26 147 PART 7 In preparing oxyalkylated derivatives of products of the kind which appear as examples in Part Six, we have found it particularly advantageous to use laboratory equipment which permits continuous oxypropylation and oxyethylation. The oxyethylatien step is, of course, the same as the oxypropylation step insofar that two low boiling liquids are handled in each instance. The oxyalkylation step is carried out in a manner which is substantially COD: ventional for the oxyalkylation of compounds having labile hydrogen atoms, and for that reason 'a detailed 'de- 75 The time regulator was set so as to inject the ethylene oxide;in approximately two hours and then continue stirring forahalf-hour or longer. The reaction went readily and,,as= a matterv of fact, the oxide was takenup almost immediately. Indeed the reaction was complete in less than an hour. More specifically it was complete in 45 minutes. The speed of reaction, particularly at the low pressure,,undoubtedly was due in a larger measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation prOducLto wit, 11.16 pounds. This represented a molal ratio of 25 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the re- -action. period was 2232. A comparatively small sample, less.than.50. grams, was withdrawn. merely for examinationtasfar as solubility or emulsifying power was concerned and also for, the purpose of making some tests on variousoil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables V and VI.

The size of the autoclave employed was 25 gallons. In

innumerable comparable oxyalkylations I have withdrawn,

a substantial portion at the end of each step and continued oxyalkylation ona partial residual sample. This was not thecase in thisparticular series. duplicated as herein after noted and subjected to oxyalkylation with a different oxide.

Example 20 This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated, the oxyalkylanon-susceptible compound, to wit, Example 1b, presentoat the beginning of the stage was obviously the same as at the end of the prior stage (Example to wit,.11.1,6 pounds. The amount of oxide present in the initial step was 11.16 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added wasanother 11.16 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 22.32 pounds and the molal ratio of ethylene oxide to resin condensate was 50.8 to 1. The theoretical molecular weight was 3348.

Themaximum temperature during the operation was 130 C. to 135 C. The maximum pressure was in the range. of to pounds. The time period was one hour.

Example 30 Theoxyla'tion. proceeded in the same manner described in Examples 10 and 2c. There was no added solventand' noadded catalyst. The oxide added was 11.16 pounds and'the total. oxide atthe end of the oxyethylation step was 33.48 pounds. The molalratio of oxide to condensate was 76.2 to- 1. Conditions as far as temperature and pressure and time were concerned were all the-same as inExamples 1c and 2c. The time period was somewhat longer than in previous examples, to wit, 2 hours.

Example 46 The oxyethylation was continued and the amount of oxide added again was 11.16 pounds. There was no added catalyst and no added solvent. molecular weight at the endofthe reaction period was 5580. The molal ratioof. oxide to condensate was, 101.6,

to 1. Conditions as far astemperature andpressure were Certain examples were.

The theoretical concerned. were the same, as; in previous examples; The time period was slightly longer, to, wit, 3 hours. The reaction unquestionably began to slow up somewhat.

Example So The oxyethylation continued with the introductionof:

another 11.16 pounds of ethylene oxide. No moresolvent was introduced but .3 pound causticv soda was added. The theoretical molecular weight at the end of the agita tion period was 6696, and the molal ratio of oxideto resin condensate was 127 to 1. The time period, how-- ever, dropped to 1V2 hours. Operating temperatureand pressure remained the same as in the previous example.

Example 60 Example 70 The same procedure was followed as in. the previous six examples without the addition of more oaustitc or more solvent. The total amount of oxide introduced: at the end of the period was 78.12 pounds. The theoretical. molecular weight at the end of the oxyalkylation period was 8928. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 3 hours Example This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 89.28 pounds. The theoretical molecular weight was 10,044. The molal ratio of oxide to resin condensate wa 203.2 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 4 hours.

The same procedure as described in the previous'exam ples are employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a l5-gallon autoclave and thenv transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables V and VI, it will be noted that compounds. 10 through 400 were obtained by the use of ethylene oxide, whereas 410 through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table V it is to be noted as follows.

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

27 The amount of condensate is shown in the third column. Assuming that ethylene oxide alone is employed, as happens to be the case in Example through 400, the amount of oxide present in the oxyalkylation derivatives is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

p The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 8th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mas withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 8 coincides with the figure in column 3.

Column 9 shows the amount of ethylene oxide employedin the reaction mass at the end of the particular period.

Column 10 can be ignored insofar that no propylene oxide was employed.

Column 11 shows the catalyst at the end of the reaction period.

Column 12 shows the amount of solvent at the end of the reaction period.

Column 13 shows the molal ratio of ethylene oxide to condensate.

. Column 14 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VIII. It is to be noted that the first column refers to Examples 10, 20, 36, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table VI, Examples 410 through 80:: are the counterparts of Examples 10 through 400, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, two columns are blank, to wit, columns 4 and 9.

Reference is now made to Table VII. It is to be noted these compounds are designated by d numbers, 14, 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the 0 series, for example, 350, 39c, 53c and 62c. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 1c through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from 350 and 390, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, those compounds obtained from 530 and 620 obviously came from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial 0 series such as 35c, 39c, 53c, and 62c, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will noted that the initial product, i. e., 350, consisted of thereaction product involving 11.16 pounds of the resin In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylation step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of the next step;

except obviously at the very start the value depends on the theoretical molecular weight at the end of the initial oxyalkylation step; i. e., oxyethylation for 1a through 16d, and oxypropylation for 17d through 32d.

' It will be noted also that under the molal ratio the values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions is. substantially the same as before and appears in Table VIII. The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particu larly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethyleneoxide and then use propylene oxide, and then go back to ethyl ene oxide; or, inversely, start with propylene oxide then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amber or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene adds nothing to the color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decolorized by the use of clays, bleaching chars etc. As far as use in demulsification is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

Generally speaking, the amount of alkaline catalystpresent is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen atom, the removal of the alkaline catalyst is somewhat more difficult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also; The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

Molec. wt. based value oxide on the oretical cmpd.

Molal ratio oxide Ethyl. Pro I.

susoeplz. suscept.

cmpd.

S01. vent, lbs:

0 0000000455555550000000055555 055000000WXU 7 7 7 7 7 7 7 .aA4 4 4A4MA TZZZ- TZA A A A A AM4MAMIZZTZZT1 Catalbs.

0000333300003333000033330.000333300003333 LLLLLLLLL1LLLLLLLLLLLLLLLLLLLLLLLLLLLLLL Composition at and Prop]. oxide. lyst;

Ethl. Oxide,

0-8 cmpd.,

lbs.

Molec. wt.

on theoretical' valuev oxide scept. cmpd;

Molol ratio Ethyl. Ptopl. based.

oxide to oxyto ox alkyl. alk suscept. su

cmpd.

Sol. vent, lbs.

000000005555555 6000000055 055515500000000 7 7 T7 7 7 7 7 4A44d dn md ZTTTZIliAImA miA uS ZZZZZTZ 11111441.1111l555111115552222255511111444 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL Composition at end oxide, lyst,

Ethl. Propl. Cataoxide,

TABLE V Solvent, lbs.

0000000055555555000000005555555500000000 7 ZZZT11144 44 4111111111114AMAI A A ATmZZTZ-LITZ Cats.-

0000333300003333000033330000333300003333 LLlLLllLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL Ethl. Prop]. oxide, oxide. lyst;

Composition before lbs.

LLLLLLLLZZZZZZZ2O 2 1 1 1 666666660000000 4 444 66666666 666 111111115555555w%uoo8ooooM%-D5555555mmmm111 00 2 11 0-8 ompd., cmpd., ex. No.

Ex. N 0.

TABLE VI Solvent, lbs.

0000000055555555000000005555555500000000 7 1111111417111411111111111A A A A A 4 AJLZ- Z- ZZ7N 111114.4411111555111115552222255511.111444 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL oxide, lyst,

Composition before Ethl. Propl. Cataoxide,

O-S" cmpd., ex. No.

*Oxyalkylation-susceptible.

Ex. No

'Oxyalkylation-susceptible.

wt. based oretical value mmmmmmmmmmmmmmmwmwmmmmmmmmmmmm 90900 I Molec.

Propl.

oxide outbaalkyl.

cmpd.

. 9 .88888888 .O.0. v mma mw mmaowmmmmmmmmmmmwmmmmmm Molal ratio slkyl. susoept. suscept.

Solvent,

00000000000000005555555500000000 7 7"7 7 7 7 ZZZZZZZZZZLiLLIII mZZZZZIZZ Composition at eml Catalyst, lbs.

00000555333388881116666655655000 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLZZZ TABLE V n Pro 1. oxi

lbs.

E thl oxide,

lbs.

cmp

lbs.

Solvent,

00000000000000005555555500000000 7 7 17 7 7 TZZTTZZ- IZATmATmLAMANiZRmTZZ-LZT Catalyst, lbs.

000000553333388811111111555555O0 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLZZ P ropl. oxide,

lbs.

Ethl. oxide, lbs.

Composition before b LLLLLLLL LLLLLLLOMZZZ 2 ZQQQQOHWQO O-S' cxnpd., cmpd., ex. No.

Ex. No.

Kerosene Insoluble. Dispersible. Soluble.

D0. Insoluble. Dis ersible.

Solubility Xylene 1% Soluble 2% do- TABLE VIII Time, hrs.

Max. pres., p. s. i.

Max.

TABLE VIII (continued) Solubility Time,

Kerosene Soluble. D o.

o. Insoluble.

Do. Dlspersible.

Solu le.

Soluble.

o. Dlsperslble. Soluble.

Do. Dispersible. Insoluble.

Dlspersible.

Insoluble.

Do. Do.

PART 8 The resin condensates which are employed as intermediate reactants are strongly basic. Initial oxyalkylation of these products with a monoepoxide or diepoxide either one can be accomplished generally, at least in the initial stage, without the addition of the usual alkaline catalyst such as those described in connection with oxyalkylation employing monoepoxides in Part 7 immediately preceding. As a matter of fact, the procedure is substantially the same as using a non-volatile monoepoxide such as glycide or methylglycide. However, during progressive oxyalkylation with a monoepoxide it is usually necessary to use a catalyst as previously described and, thus, there may or may not be suflicient catalyst present for the reaction with the diepoxide. Reference to the catalyst present includes the residual catalyst remaining from the oxyalkylation step in which the monoepoxide was used.

Briefly stated then, employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials, such as caustic soda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind illustrated by iron and tin chloride. Furthermore, insoluble catalyst such as clay or specially prepared mineral catalysts have been used.- If for any reason the reaction does not proceed rapidly iii] enough with the diglycidyl ether or other analogous reactant then a small amount of finely divided caustic soda or sodium methylate can be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes without saying that the reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethyleneglycol, or the diethylether or propyleneglycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solventfree and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, then Xylene or an aromatic petroleum solvent will serve. If the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not oxyalkylation-susceptible. It is easy enough to select a suitable solvent if required-in any instance but, everything else being equal, the solvent chosen should be the most economical one.

Example 1a The product was obtained by reaction between the diepoxide previously described as diepoxide 3A and oxyalkylated resin condensate 1c. Oxyalkylated condensate has been described in previous Part 7 and was obtained by the oxyethylation of condensate 1b. The preparation of condensate lbwas described in Part 6, preceding. Details have been included in regard to both steps. Condensate 1b, in turn, was obtained from diethylamine and Resin 2a; Resin 2a, in turn, was obtained from par atertiarybutylphenol and formaldehyde.

In any event, 223 grams of the oxyalkylated resin condensate previously identified as 1c were dissolved inapproximately an equal weight of xylene. About 2 grams of sodium methylate were added as a catalyst so the total amount of catalyst present, including residual catalyst from the prior oxyalkylation, was about 2.4 grams. 17 grams of diepoxide 3A were mixed with an equal weight of xylene. The initial addition of the diepoxide solution was made after raising the temperature of the reaction mass to about 105 C. The diepoxide was added slowly over a period of one hour. During this time the temperature was allowed to rise to about 126 C. The mixture was allowed to reflux at about 132 C. using a phase-separating trap. A small amount of xylene was removed by means of a phase-separating trap so the refluxing'temperature rose gradually to about 150 C. The mixture was refluxed at this temperature for about 4 hours. At the end of this period the xylene which had been removed by means of the phase-separating trap was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on a hot plate in order to examine the physical properties. The material was an amber, or

0 Part 1 of U. s. Patent No. 2,602,062, dated July 1, 1952.-

reddish amber, viscous liquid. It was insoluble in water; it was insoluble in gluconic acid; but it was soluble in xylene and particularly in a mixture of xylene and 20% methanol. However, if the materialwas dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in a xylene-methanol mixed solvent as previously described, with or without the further addition of a little acetone.

Generally speaking, the solubility of these derivatives is in line with expectations by merely examining the solubility of the preceding intermediates, to wit, the oxyalkylated resin condensates prior to treatment with the diepoxide. These materials, of course, vary from exbut xylene-soluble or even kerosene-soluble due to high stage oxypropylation. Reactions with diepoxides or polyepoxides of the kind herein described reduce the hydrophile properties and increase the hydrophobe properties, i. e., generally make the products more soluble in kero: 'sene or a mixture of kerosene and xylene, or in xylene, but less soluble in water. Since this is a general rule which applies throughout,for sakeof brevity future reference to solubility will be omitted.

The procedure employed, of course, is simple in light of what has been said'previously and in effect is a procedure similar to that employed in the use of glycide or methylglycide as oxyalkylating agents. See, for example,

to De Groote.

Various examples obtained in substantially the same manner are enumerated in the following tables:

TABLE IX Ex. Oxy- Amt, Diep- Amt, Catalyst Xy- Molar Time of Max. No. resin congrs. oxide grs. (NaO CH3), lone, ratio reaction, temp., Color and physical state densate used grs. grs. hrs.

223 3A 17 2. 4 240 2:1 4 150 Viscous reddish amber mass. 375 3A 17 3. 9 392 2: 1 4 148 D0. 271 3A 8. 5 2. 8 280 2:1 4 145 Do. 377 3A 8. 5 3. 9 386 2:1 4 142 Do. 113 3A 1.7 1. 2 115 2:1 3 Do. 335 3A 17 3. 5 352 2: 1 4 D0. 375 3A 17 3. 9 392 2:1 4 148 D0. 271 3A 8. 5 2. 8 280 2:1 4 146 Do. 314 3A 8. 5 3.2 323 2:1 4 Do. 353 3A 8. 5 3. 7 372 2:1 4. 5 150 D0. 391 3A 17 4.1 408 2: 1 4. 5 152 Do. 279 3A 8. 5 2. 9 288 2:1 4 148 Do. 363 3A 8. 5 3. 7 372 2:1 4. 5 150 D0. 100 3A 1.7 1.0 102 2:1 3 150 D0. 152 3A 1. 7 1. 5 154 2: 1 4 152 D0.

TABLE X Ex. Oxy- Amt., Diep- Amt, Catalyst Xy- Molar Time of Max. No. resin congrs. oxide grs. (NaOCHa), lene, ratio reaction, temp., Color and physical state densate used grs. grs. hrs. C.

223 B1 27. 5 2.5 251 2:1 4 153 Viscous reddish amber mass. 375 B1 27. 5 4. 0 403 2: 1 4 152 Do. 271 B1 13. 8 2. 9 291 2:1 4 158 D0. 377 131 13.8 4.0 397 2: 1 4 154 D0. 113 B1 2. 8 1. 3 1% 2:1 3 150 Do. 335 B1 27. 5 3. 6 363 2: 1 4 150 Do. 375 B1 27. 5 4.0 403 2: 1 5 155 D0. 271 B1 13. 8 2. 9 291 2: 1 4 155 D0. 314 B1 13. 8 3. 3 334 2: 1 4 158 D0. 363 B1 13. 8 3. 8 383 2: 1 4 160 Do. 391 B1 27. 5 4. 2 419 2: 1 4 157 Do. 279 B1 13. 8 3. 0 299 2:1 4 156 Do. 363 B1 13. 8 3. 8 383 2:1 4 156 D0. 100 B1 2. 8 1. 1 113 2: 1 3. 5 150 D0. 152 B1 2. 8 1. 6 2:1 4 150 D0.

tremely water-soluble products due to substantial oxy-j ethylation, to those which conversely are water-insoluble TABLE XI Prob. mol. Ex. No. Oxyalkyl. weight of Amount of Amount of resin conreaction product, grs. solvent densate product TABLE XII Prob. mol. Ex. No. Oxyalkyl. weight or Amount of Amount oi resin conreaction product, grs. solvent densate product At this point it may be desirable to direct attention to two facts, the first being that we are aware that other diepoxides free from an aromatic radical as, for example, epoxides derived from ethylene glycol, glycerin, or the like such as the following:

may be employed to replace the diepoxides herein described. However, such derivatives are not included as part of the instant invention.

At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethylether of ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent, such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance, 90% to 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either-the resin molecule or the diepoxide molecule actually may vary from the true molecular weight by several percent.

The condensate can be depicted in a simplified form which, for convenience, may be shown thus:

(Amine)CH2(Resin)CI-I2(Amine) If such product is subjected to oxyalkylation reaction in 38 volves the phenolic hydroxylsof the resin structure and, thus, can be depicted in the following manner:

(Amine) CH2 Oxyalkylated Resin) CH2 (Amine) Following such simplification the reaction with a polyepoxide, and particularly a diepoxide, would be depicted thus:

(Amine) OHflOxyalkylated Resin) OH (Amine) (Amine) OH2 OXY811Y18lt8d Resin) OHAAr-nine) in which D. G. E. represents a diglycidyl other as specified.

As has been pointed out previously, the condensation reaction may produce other products, including, for example, a product which may be indicated thus in light of what has been said previously:

[(Amine)CHz(Resin)] This product, since it is susceptible to oxyalkylation by means of the oxyalkylated phenolic hydroxyl groups and depending on the selection of the amine, may be susceptible to oxyalkylation in event a hydroxylated amine or polyamine had been used, and may be indicated in the following manner:

[Oxyalkylated (Amine CH2(Resin When a. digly cidyl other is employed one would obviously obtain compounds in which two molecules of the kind described immediately preceding are united in a manner comparable to that previously described, which may be indicated thus:

I Oxyalkylated (Amine) CHAResin) D.G.E.

l Oxyalkylated (Amine)CH (Resin) Likewise, it is obvious that the two difierent types of oxyalkylation-susceptible compounds may combine so as to give molecules which may be indicated thus:

I (Amine)OHg(Oxyalkylated Resin)CH (Amine) D.G.E.

Oxyalkylated (Amine) OHKResin) Oxyalkylated (Amine) C H: (Amine) D.G.E.

l l l (Amine)CH (Oxyalkylated Resin)OH (Amine) l O'xyalkylated(Aruine)CHflAmine) I D.G.E.

Oxyalkylated(Amine) CH (Resin) 39 suitable method of characterizing the final reaction product except in terms of method of manufacture.

PART 9 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such. as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be empoyed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the re fining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

' It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or ina form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent in solubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

In practicing the present process, the treating or demulsifying agent is used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-hold demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mix ture to stratify.

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. For instance, by mixing 75 parts by Weight of an oxyalkylated derivative, for example, the product of Example Be With 15 parts by Weight of xylene and 10 parts by weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and of course will be dictated in part by economic considerations, i. e., cost.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

Oxyalkylated derivatives, for example, the product of Example 3e, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

' Isopropyl alcohol, 5%

The above proportions are all weight percents.

Having thus described our invention what we claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being obtained by athree-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide; said first manu'facturing step being amethod of (A) condensing (a) an oxyalkylation susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with theproviso that the resinous condensation product resulting from the process be heat stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and then completing the reaction by a third step of (C) reacting said oxyalkylated resin condensate with a phenolic polyepoxide free from reactive functional groups other than epoxy and hydroxyl groups and cogenerically associated compounds formed in the preparation of said polyepoxides; said epoxides being monomers and low molal polymers not exceeding the tetramers; said polyepoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues fromed by the elimination of the kctonicoxygen atom, and aldehyde residues obtained by the elimination of the aldehyde oxygen atom, the divalent radical the divalent radical, the divalent sulfone radical, and divalent monosulfide radical S, the divalent radical -CH2SCH2-, and the divalent disulfide radical SS, said phenolic portion of the polyepoxide being obtained from a phenol of the structure consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER; SAID DEMULSIFIER BEING OBTAINED BY A THREE-STEP MANUFACTURING PROCESS INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A MONOEPOXIDE; AND (3) OXYALKYLATION WITH A POLYEPOXIDE; SAID FIRST MANUFACTURING STEP BEING A METHOD OF (A) CONDENSING (A) AN OXYALKYLATION SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOLALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 